Glass article



Patented June 17, 1947 UNITED? "ST TES PAT GLASS-ARTICLE Robert H. Dalton, Corning, N. Y., as..." to

Corning Glass Works, Corning, N.- Y., a corporation of New York p No Drawing. Original 1941, Serial No. 386,190. Divided and this anplication September 10, 1942, Serial No. 457,884

3 Claims. (Ci. 49-92) This invention relates to glass and methods of producing color therein and more particularly to application March '31,

pie, the coloration sue to heattreatment will thereafter occur at a lower temperature and/or in a shorter time than it otherwise would and glasses which would not normally become colored will, when so irradiated, developcoloration on heat treatment.

The initial effect of irradiation insome cases is the development of a blue color in the irradiated portion of the glass without the application of heat. This is not believed to be dueto copper in the ordinary oxidized state since the spectral solution inthe form of a coppersilicate. When such glasses are melted reducingly through the use of reducing agents in the batch they are, provided the copper content be sufficiently low,-substantially colorless, particularly if cooled rapidly,

but under proper conditions they will become red when they are reheated. Under these circumstances the glasses are believed to contain colloidal copper or cuprous oxide and are referred to in general as copper ruby glasses. The tendency of copper ruby glasses to develop color varies with composition, with the rate of cooling of the glass when fabricated into ware and with the time and temperature of heat treatment. A composition containing a small amount of tin oxide-is more heat sensitive than one containing no tin oxide. 4

One object of this invention is to increase the sensitivity to reheating of reduced copper containing glasses.

Another object is to render such glasses selectively heat sensitive whereby an article thereof has certain portions which are more sensitive to reheating than other portions, thereby permitting the production ofa design in the glass.

A further object is to produce a glam article composed throughout of a single copper containing glass which is selectively colored.

Another object-is to prevent opalescence in cop per ruby glasses 'due to the formation of too coarse a colloid.

Still another object is to produce colored glass fibres.

Another object is to produce photographic images in glass.

To these and other ends the invention includes the articles and methods to be hereinafter more fully described and claimed.

I have discovered that exposure to short wave radiations will increase the heat sensitivity of reduced copper ruby glasses while in the colorless state. In other words, if such glasses are thus irradiated with a quartz mercury arc, for examcharacteristics of the irradiated glass are quite different-from those of an oxidized copper-corntaining glass.

When the irradiated glass is subsequently heated to a temperature in the neighborhood. of its annealing temperature, the irradiated portion acquires the red color characteristics of copper ruby glasses, especially if the glass contains a substantial amount of tin oxide. However, the initial development of the blue color is independent of the presence of tin inthe. glass.

' In practicing the invention a glass batch con- 'taining copper equivalent to at least .05% CuzQ as in the finished glass and containing a reducing by trial.

1 shorter as the copper content of the glass is inagent and preferably also a small amount of tin oxide isv melted and fabricated in the usual manner. The glass article is then irradiated preferably by means of a mercury are for the proper length of time which may readily be determined In general, the time required will be creased, but with too high copper content it may be diflicult to retain the glass in the initial colorless state on cooling,'particularly in the case of thick were wherein the retention of heat on cooling may furnish the heat treatment required to develop the color. With thin ware or articles which can be cooled rapidly, relatively high copper contents can be used and the time of irradiation thereby shortened. For example, glass fibres containing about 1% of CllrO which are initially colorless, on being irradiated for ten seconds or more, become light blue and onsubsequent heat treatment become red. Without being irradiated no color can be obtained by the heat treatment, because oxidation by the air takes place before the color can develop,

Reduced copper containing glass in the colorless state fluoresces in ultra-violet light. Continuous exposure will gradually diminish such fluorescence and, if the glass is subsequently heated until th ruby color develops, the ability to flusnr omen v articles.

istic of the copper only while in a state of solu tlon in the glass and not when it is in the ruby colored colloidal state.

In an article in which only a portion of the glass was irradiated the development of the red coloration in-the irradiated portion occurs before the unexposed portion is aflected. By shielding selected portions of the article from the radiations, only those parts which were exposed become colored and hence designs may be produced on the article which may be blue or red, depending on whether the irradiation is followed by a heat treatment. Cloth made of glass fibres can be provided with a variety of designs after it is fabricated, such designs being blue and/or red in color as above described. The article to be treated may'consist of a flashed glass, that is, one comprising a thin layer of a copper-containing glass fused to another glass.

Inasmuch as the time required for the irrradiation varies with the type of glass as well as with the copper content, a time suitable for all glasses cannot be stated but for an individual glass it can readily be determined by trial. Glasses which do not readily develop color in heat treatment are particularly suitable for the production of designs in accordance with the invention because even relatively thick pieces can be obtained in the colorless state without resorting to a special chilling technique. Moreover, since the effect of irradiation depends on the action of short wave radiations, for example, ultra-violet light, on the copper contained in the glass, it is an advantage to use a glass which at least partially transmits such radiation.

Without limiting the invention thereto, the following batches are given as examples of glasses which may be employed:

In the above batches sodium cyanide and abietic acid are used as reducing agents. Other known reducing agents may be employed. Batch 1 which contains no tin is suitable for the production of a blue coloration by irradiation but does not develop a. satisfactory red coloration when subsequently reheated. Batches 2, 3 and 4 are suitable for the production of both red and blue colorations. Batch 4 is particularly suit able for use for glass fibres and thin walled active radiation and printing through the same on the glass. This process can be effectively carried out by coating a, copper-containing glass ditainlng throughout a reduction product of C110" rectly with a photographic emulsion similar to that used ona Schumann plate, making a. negative on this emulsion in the conventional s-ianner, irradiating the glass through this negative as previously described, removing-the emulsion, and heat treating the glass to develop a ruby colored image therein. Insofar as I know, irradiation is the only method which will produce in the above described glasses a latent image capable of being developed by subsequently heating the glass. In the absence of a more appropriate term, the word irradiated is used in the claims to define the glass article containing such a, latent image.

It is also possible to produce an image directly in the glass by illuminating an object with short wave radiation, focusing the image thereof on the glass and subsequently heat treating to develop the color. I

In general, copper containing glasses irradiated by my method have less tendency for the color to develop with an opalescent or clouded appearance than similar glasses colored without preliminary irradiation.

I claim:

1. An article composed throughout of a single glass containing copper equivalent to at least .05% C1120 and having a heat stable picture exhibiting photographic detail formed in the glass in various shades of color of one hue.

2. An article comprising a reduced glass con,-

by means of which predetermined parts of the glass are colored blue, the remainder of the glass being substantially colorless, the colored parts forming a photographic image within. the glass mass.

3. An article comprising a substantially colorless reduced glass containing an irradiated reduction product of CuO and having within its mass a predetermined, latent, photographic image capable of being developed as a permanent red coloration in a clorless glass body by uniformly heating the entire glass body.

ROBERT E. DALTON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,169,571 Rosenthal Jan. 25, 1916 10,446 Locke Feb. 5, 1884 366,364 Atterbury July 12, 1887 2,314,804 Willson Mar. 23, 1943 282,002 Locke July 24, 1883 402,090 Leighton Apr. 23, 1889 2,075,446 Leibig Mar. 30, 1937 2,326,012 Dalton Aug. 3, 1943 FOREIGN PATENTS Number Country 7 Date 4,881 1 Great Britain 187 4,880

Great Britain 18 78 

